ライフサイエンスコーパス: diyne

1 groups in the biscarbene complex and in the diyne.

2 gments for the sp2 CH fragment, of 3-ene-1,5-diyne.

3 ery high site selectivity in a coupling of a diyne.

4 lar ring closure reaction of a nonconjugated diyne.

5 ting cooperative binding of both ends of the diyne.

6 ld moieties from one dibenzopentalene to one diyne.

7 zeroth order in nitrile, and zeroth order in diyne.

8 -carbonyl complex on the conjugated enyne or diyne.

9 xa-1,2,3,5-tetraenes, and (Z)-hexa-3-ene-1,5-diynes.

10 approach to the synthesis of symmetrical 1,4-diynes.

11 ed cross-benzannulation of cyclic enynes and diynes.

12 into the corresponding monoalkylated NPT 1,6-diynes.

13 he substituents at the alkyne termini in 1,3-diynes.

14 u-catalyzed intramolecular hydroarylation of diynes.

15 of readily available pyrazolidinones and 1,3-diynes.

16 odkiewicz coupling to produce functionalized diynes.

17 antiaromatic boroles with 1,4-diarylbuta-1,3-diynes.

18 regioselectivity is found with unsymmetrical diynes.

19 imethyl carbonate to produce unsymmetric 1,3-diynes.

20 native cyclization of N-tosylated enynes and diynes.

21 for the cycloaddition of various ketenes and diynes.

22 enynes but diminishes to 0.5-2 kcal/mol for diynes.

23 that are generated in the cyclization of the diynes.

24 desymmetrization of unprotected tert-hydroxy diynes.

25 es of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy,

26 hynylbenzene derivative to an organometallic diyne (1,2-diethynyl-3,4-bis(trimethylsilyl)cyclobutadie

27 idyl)ethynyl)bicyclo[2.2.2]oct-1-yl)buta-1,3-diyne, 1, contains two 1,4-bis(ethynyl)bicyclo[2.2.2]oct

28 ization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dip

29 nylphenyl)methylammonium (BMAA) and buta-1,3-diyne-1,4-diylbis(4,1-phenylene)dimethylammonium (BDAA)

30 nal functionalization of the known hepta-2,5-diyne-1,7-diol by partial reduction of the two triple bo

31 7 and 29 was accomplished from the key diene-diynes 11 and 19b.

32 hese conditions, conversion of acyclic diene-diyne 16 into tetracyclic system 17 was achieved in 74%

33 Reductive cyclization 1,6-diyne 1a and 1,6-enyne 10a performed under an atmosphere

34 f carbon-, nitrogen- and oxygen-tethered 1,6-diynes 1a-9a and 1,6-enynes 10a-18a using cationic Rh(I)

35 ystems, (E)-1,3,4,6-tetraphenyl-3-hexene-1,5-diyne (1a) and (E)-3,4-bis(4-iodophenyl)-1,6-diphenyl-3-

36 -bis(4-iodophenyl)-1,6-diphenyl-3-hexene-1,5-diyne (1b), is decreased by nearly half on a Au(111) sur

37 e isomeric diazo compounds, 1-diazo-hexa-2,4-diyne (2) or 2-diazo-hexa-3,5-diyne (3), generates tripl

38 lly initiated topochemical polymerization of diynes 3 and 4a-c in the crystal.

39 The diynes 3,3',5,5'-tetramethyl-4,4'-di(pent-1-ynyl)bipheny

40 diazo-hexa-2,4-diyne (2) or 2-diazo-hexa-3,5-diyne (3), generates triplet carbene 1.

41 sis of (3R,4E,16E,18R)-icosa-4,16-diene-1,19-diyne-3,18-diol, isolated from Callyspongia pseudoreticu

42 ompounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skel

43 pound as (3 S,8 R,9 R,E)-heptadeca-10-en-4,6-diyne-3,8,9-triol, and develop a modular asymmetric synt

44 s but the biosynthesis of their defining 1,5-diyne-3-ene core moiety remains largely enigmatic.

45 ynes are structurally characterized by a 1,5-diyne-3-ene motif within a 9- or 10-membered enediyne co

46 The (Z)-hex-1,5-diyne-3-ene reactive core common to the enediyne antitum

47 ow report that cyclohexeno[3,4]cyclodeca-1,5-diyne-3-ene rearranges to its automer, via a D(2h)-symme

48 For instance, diyne 6 reacted with dipropylacetylene to give paracyclo

49 For example, diyne 6 reacted with p-tolunitrile in 1,4-dioxane to giv

50 enerated via chemoselective hydroboration of diyne 6 with diisopinocampheylborane.

51 1,2-hydrogen migration to form hex-1-ene-3,5-diyne (6).

52 m the all-carbon analogue, (Z)-hex-3-ene-1,5-diyne (7), the parent molecule for the Bergman cyclizati

53 clusively (44p:44m > 50:1) in 64% yield from diyne 8 and 2-phenylethylisocyanate.

54 t involve reductive coupling of enyne 1a and diyne 9a under an atmosphere of elemental deuterium corr

55 ed hydrogenation of 1,3-enynes 1a-8a and 1,3-diynes 9a-13a at ambient temperature and pressure in the

56 The diyne alcohol 10 was transformed regio- and stereoselect

57 als with bis(pyridyl)oxalamides in which the diyne alignment is near the ideal parameters for topoche

58 ycloaddition of alkynes with fluorinated 1,7-diyne amides gave 4,4-difluoro-1,4-dihydro-3(2H)-isoquin

59 Here, we show that diyne amphiphiles with carbohydrate headgroups can be as

60 + [2+2+2] sequence using a silyl-substituted diyne and 2 equiv of the corresponding alkyne-nitrile ha

61 between 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne and 9-methylanthracene, such that the bulky methyl

62 bonding may play a role in preorganizing the diyne and alkyne coupling partners for establishing the

63 The position of the diyne and chain length affect the self-assembling proper

64 mplex is the active species within which the diyne and diynophile engage to produce the benzyne.

65 ng on the nature of the atoms connecting the diyne and diynophile, reaction temperatures of ca. 80-13

66 hain lengths, substituents, and positions of diyne and studied their self-assembling properties in se

67 e semihydrogenation of internal alkynes, 1,3-diynes and 1,3-enynes.

68 of deuterium was achieved in the case of 1,3-diynes and 1,3-enynes.

69 Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ri

70 The in situ method also converts diynes and carbon dioxide to the corresponding pyrones.

71 Diynes and cyanamides undergo an iron-catalyzed [2 + 2 +

72 y this procedure to furnish a library of 1,3-diynes and enynes in high yields.

73 Diynes and enynes were used as coupling partners.

74 ve Ni0/NHC catalyst for the cycloaddition of diynes and nitriles that affords pyridines without a dec

75 ation of pyridines from the cycloaddition of diynes and nitriles.

76 topic to gain knowledge on the reactivity of diynes and to systematise the range of information relat

77 variety of internal alkynes including enyne, diyne, and ynamide and more challenging terminal alkynes

78 ally activated y-Al(2)O(3) activates enynes, diynes, and arene-ynes in a manner enabling reactions th

79 plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transfor

80 loped protocol involves the synthesis of 1,3-diyne-anilines followed by a one-pot gold(I)-catalyzed d

81 Though the penta-1,4-diyne anion exhibits a large cyclization barrier of +66

82 zation: electrocyclizations of the penta-1,4-diyne anion, hepta-1,6-diyne cation, and octa-1,7-diyne

83 balt(II) catalyzed C-H functionalization/1,3-diyne annulation under mild conditions to afford 40 alky

84 olute regiospecific control when symmetrical diynes are applied.

85 seful synthetic handles, and 3-amino skipped diynes are convenient building blocks for enantioselecti

86 bered aryl-substituted ynamides with various diynes are described here.

87 or preparing neopentylene-tethered (NPT) 1,6-diynes are described.

88 steric effects, while conjugated enynes and diynes are predicted to have increased reactivity and ve

89 These NPT 1,6-diynes are valuable pai-systems for reaction discovery a

90 mination of aniline by employing o-amino 1,6-diyne as a potential starting material.

91 as the nitrogen source and activated skipped diynes as the electrophilic reactive partners in a coupl

92 S, Se, Te) bond to the triple bond(s) in the diyne, as well as to the type of the reagent used, and t

93 SO system allows cyclization with conjugated diynes at room temperature.

94 riad of merits offered by a synthesized aryl-diyne-based Raman tag such as excellent photostability,

95 o-Diels-Alder (HDDA) reaction converts a 1,3-diyne bearing a tethered alkyne (the diynophile) into bi

96 diastereoselective cycloisomerization of 1,6-diynes bearing an alkylidene cyclopropane moiety has bee

97 Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to alpha-ketols (alpha-hydroxyke

98 was observed to result in the 1,11-dien-3,9-diyne benzoate undergoing a more rapid tandem 1,3-acylox

99 d double cycloisomerization of 1,11-dien-3,9-diyne benzoates is described.

100 atalyzed cycloisomerization reactions of 1,7-diyne benzoates to prepare indeno[1,2-c]azepines and aza

101 s of cis-1,8-bis(pyridin-3-oxy)oct-4-ene-2,6-diyne (bpod, 1), [Cu(bpod)(2)]PF(6) (2), and [Cu(bpod)(2

102 alized over the 1,4-di(pyridin-4-yl)buta-1,3-diyne bridges that provide a pathway for electronic comm

103 Rh/tfb complex as the catalyst, and not only diynes but also triynes and tetraynes could be polymeriz

104 is-styrenyl bromides lead to unsymmetric 1,3-diynes by the cross coupling of terminal alkyne and the

105 ped for the functionalization of various 1,3-diynes by the hydrosilylation reaction with triethyl- or

106 Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bo

107 )-] (formed by coordination of bi-functional diynes: C[triple bond, length as m-dash]C, C[triple bond

108 (formed by coordination of two bi-functional diynes: C[triple bond, length as m-dash]C, C[triple bond

109 cally coupled triple bonds of conjugated 1,3-diynes can be faithfully discriminated as long as one of

110 /cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described.

111 l mol(-1), cyclization of both the hepta-1,6-diyne cation and octa-1,7-diyne dication along a previou

112 ions of the penta-1,4-diyne anion, hepta-1,6-diyne cation, and octa-1,7-diyne dication, leveraging th

113 al and achiral tubule-forming molecules, the diynes centered in their hydrocarbon tails.

114 g method using rationally synthesized phenyl-diyne cholesterol (PhDY-Chol) and stimulated Raman scatt

115 of unprecedented tetracopper(I) mu-acetylide/diyne complexes that were characterized by NMR and UV/Vi

116 through the convergent coupling of a common diyne component with appropriate AB-ring aldehydes, a st

117 tolerance and leads to a broad range of 1,3-diyne compounds in moderate to excellent yields using lo

118 Reaction of a mesityl-terminated diyne containing a rigid dihexylfluorenylene spacer with

119 Linear oligophenylene diynes containing 6, 9, and 12 phenylene rings were synt

120 the nitrile, either 3,4-pyridynes (from 1,3-diynes containing a tethered cyano group) or 2,3-pyridyn

121 Late stage coupling of diynes containing the respective natural product FG ring

122 e report here studies of the 4-aza-3-ene-1,6-diyne-containing benzimidazolium salt AZB002 [1-methyl-2

123 and Fmoc-protected derivatives of enyne and diyne coupling products 14b-16b occurs in excellent yiel

124 Platinum-catalyzed diyne cyclization/hydrosilylation tolerated a range of f

125 ted 1,2-dialkylidenecyclopentanes formed via diyne cyclization/hydrosilylation underwent a range of t

126 s a one-pot sequential Zr-mediated oxidative diyne-cyclization/regioselective opening sequence for pr

127 includes inter- and intramolecular buta-1,3-diyne cyclizations with the formation of iodoethynylhete

128 nute advantage for a concerted process; many diyne cycloadditions or aryne cycloreversions will proce

129 enediamine derivative (4) containing a 10,12-diyne-diacyl domain was treated with DTPA anhydride foll

130 both the hepta-1,6-diyne cation and octa-1,7-diyne dication along a previously unreported triplet pat

131 anion, hepta-1,6-diyne cation, and octa-1,7-diyne dication, leveraging the spin-flip formulation of

132 Experimental studies on intramolecular diyne + ene cycloadditions show two distinct reaction pa

133 benzenes was accomplished via gold-catalyzed diyne-ene annulation.

134 zed intermolecular condensation of amine and diyne-ene, we report herein the first example of enantio

135 by gold-catalyzed cycloisomerization of 1,6-diyne esters is described.

136 dimethoxy-substituted 3,4-benzocyclodeca-1,5-diyne followed by oxidative demethylation.

137 directly gives the sigma,pi-gold coordinated diyne for the further intramolecular cyclization reactio

138 ehydro-Diels-Alder reaction of (E)-3-ene-1,8-diynes for the preparation of isoindolines, dihydroisobe

139 2] annulation of N-chlorobenzamides with 1,3-diynes for the synthesis of 3-alkynylated isoquinolone d

140 Using ruthenium(0) catalysts, 1,6-diynes form ruthenacyclopentadienes that engage transien

141 2.2]octane (BCO) chiral rotators linked by a diyne fragment and self-assembles in a one-dimensional,

142 udes (i) the enantioselective synthesis of a diyne fragment containing the steroidal A/B rings, (ii)

143 ction to synthesize a single Sondheimer-Wong diyne from 6,13-dibromopentaleno[1,2-b:4,5-b']dinaphthal

144 The reaction of unsymmetrical alpha,omega-diynes gave a product only with the substituent adjacent

145 s and subsequent [4 + 2] benzannulation with diynes gives tetrasubstituted benzenes in moderate to go

146 The phenyl-diyne group is biologically inert and provides a Raman s

147 nsitive to the position of the polymerizable diyne group; thus, the polymerization process, typically

148 oited in the transformation of acetylide and diyne groups to a variety of substrates, or as a startin

149 ng-range carbon atom topomerization in a 1,3-diyne has been demonstrated for the first time.

150 e cross-coupling of alkynes to unsymmetrical diynes has been achieved for the first time.

151 annulation of N-(7-azaindole)amides with 1,3-diynes has been demonstrated.

152 arbonylanilines and ynamide-derived buta-1,3-diynes has been reported.

153 C-H activation/annulation reactions with 1,3-diynes has remained an intriguing challenge.

154 ive enyne CM and RCM reactions involving 1,3-diynes have been developed.

155 es and a smaller number of examples with 1,3-diynes have been reported.

156 A series of trans-enynes and unsymmetric 1,3-diynes have been synthesized by this protocol.

157 further studies of the cycloaddition of 1,3-diynes in addition to click chemistry.

158 he formation of macrocycles from alpha,omega-diynes in cobalt-mediated co-cyclotrimerization reaction

159 giving the desired cross-coupled conjugated diynes in excellent heteroselectivity (>10:1), in good t

160 es to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functio

161 ariety of synthetically useful unsymmetrical diynes in good yields.

162 reductive elimination produces a variety of diynes in high yields.

163 re described from elemental selenium and 1,3-diynes in superbasic media.

164 The utility of substituted NPT 1,6-diynes in target-oriented synthesis is noted herein.

165 Hydrogenation of 1,6-diynes in the presence of alpha-ketoesters provides anal

166 ltrialkylstannes (R(3)Si-SnR'(3)) add to 1,6-diynes in the presence of Pd(0) and tris-pentafluropheny

167 nsubstituted 1-phenyl-4-aryl-3-aza-3-ene-1,4-diynes in which the aryl group is phenyl, o-(methoxy)phe

168 data for a number of different tethered yne-diynes, indicates that the reaction proceeds in a highly

169 ross-coupling reaction producing the desired diyne intermediate 10, while the corresponding omega-est

170 The reactions of enynes and diynes involve 1,4-attack of the Ni-carbonyl complex on

171 ology, a 16-membered cobalt-complexed cyclic diyne is available in 28% yield over eight steps (an ave

172 the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'd

173 ingle isomeric benzyne is formed when a Bpin-diyne is used; this selectivity is rationalized by the g

174 mode of cascade arylative cyclization of 1,6-diynes is disclosed using dibenzoxaborin as an arylating

175 On the other hand, dialkyl-1,3-diynes led to the selective formation of C2-alkynylated

176 to generate a structurally rigid, linear 1,3-diyne linkage has been known for over a century.

177 equential enyne ring-closing metathesis of a diyne moiety and metallotropic [1,3]-shift followed by a

178 f the incipient p-benzyne diradical across a diyne moiety of the macrocyclic ring affords an aromatic

179 ydrolytic instability of the 3-aza-3-ene-1,5-diyne moiety prevents its use in pH-triggered DNA cleavi

180 le systems incorporating the 4-aza-3-ene-1,6-diyne moiety were developed.

181 ration with optional saponification produces diyne monoester 15 or monoacid 3, which can be further f

182 zation, they control the spacing between the diyne monomers to produce an ordered polymer.

183 cycloalkene due to the single cyclization of diyne monomers.

184 The generation of pyridynes from diyne nitriles is reported.

185 I)-mediated oxidative cyclization of the 1,6-diyne or 1,6-enyne substrates to afford (hydrido)Rh(III)

186 The reaction of dodec-11-ene-1,6-diynes or their heteroatom congeners with a hydrosilane

187 d-chelate lipid and a commercially available diyne-PE was formulated as a liposome suspension and irr

188 38, and 40 were prepared from similar diene-diyne precursors via the tandem Pauson-Khand cyclization

189 tial intramolecular oxidative cyclization of diyne produces the nickelacyclopentadiene intermediate.

190 tion of aromatic sulfoxonium ylides with 1,3-diynes providing useful substituted 1-naphthol derivativ

191 The diynes required for this procedure are readily synthesiz

192 First, the formation of a diyne species via Glaser-Hay coupling of a terminal ynam

193 The presence of two triple bonds in the diyne structure makes these compounds important reagents

194 opyl aryl substituent to either the enyne or diyne substrate.

195 These diene-diyne substrates are found to undergo a highly chemosele

196 ition and cyclization reactions of enyne and diyne substrates assembled on a tert-butylsulfinamide ly

197 ty patterns observed with different types of diyne substrates in gold catalysis are discussed.

198 ic quantities of amino-substituted enyne and diyne substrates to ((iPr(TB))PDI)Fe(N2)2 resulted in is

199 Diynes synthesized by this methodology were readily zirc

200 st an unprecedented oxidative cyclization of diynes takes place.

201 1-Phenyl-4-aryl-3-aza-3-ene-1,5-diynes that lack a 6-substituent undergo aza-Bergman cyc

202 Diynes that possessed an electron-deficient internal alk

203 Diynes that possessed propargylic substitution underwent

204 ranging from 80% to 89%, whereas icosa-5,15-diyne (the dimer obtained from a 1-halo-5-decyne) is fou

205 ution on the cycloaromatization of 3-ene-1,5-diynes (the Bergman cyclization).

206 selectivity inherent to these chiral skipped diynes, the reaction tolerates an extremely broad substr

207 ther symmetrical or unsymmetrical conjugated diynes through homo-coupling or cross-coupling.

208 the oxidative addition of an interlocked 1,3-diyne to a rhodium(I) center.

209 he Bergman cyclization of (Z)-hexa-3-ene-1,5-diyne to form the aromatic diradical p-benzyne has garne

210 e thermal cyclization of an alkyne and a 1,3-diyne to generate a benzyne intermediate.

211 amolecular propargylic ene reaction of a 1,6-diyne to generate a vinylallene, which then reacts in an

212 elective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures.

213 d for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zi

214 A new asymmetric [2+2+2] cycloaddition of diynes to sulfonimines under rhodium catalysis that prov

215 A Ni/N-heterocyclic carbene catalyst couples diynes to the C(alpha)-C(beta) double bond of tropone, a

216 [3+2] cycloadditions, and polymerization of diynes, triynes, dienes, trienes, and quinodimethanes, e

217 ross-benzannulation of conjugated enynes and diynes under cobalt-catalysis led to 1,2,3-trisubstitute

218 A cool break: 3-Azetidinone and a variety of diynes undergo a cycloaddition reaction catalyzed by Ni/

219 For example, 3-aza-3-ene-1,5-diynes undergo an aza-Bergman cyclization to afford the

220 In co-crystals with one oxalamide host, the diyne undergoes spontaneous topochemical polymerization

221 Long-chain alpha,omega-diynes underwent metal-mediated [2 + 2 + 2] cycloadditio

222 nnulenes incorporating strained 1,4-buta-1,3-diyne units have been synthesized, where m = 2, n = 14 (

223 ke nanoribbon (GDNR) bearing both alkyne and diyne units, allowing for multichannel pi-conjugation, w

224 cloaddition with substrates containing three diyne units.

225 nzo[g]indoles has been discovered from azido-diynes using InCl(3) as catalyst.

226 yzed synthesis of nonracemic 3-amino skipped diynes via an enantiodetermining C-C bond formation is d

227 t silver-catalyzed desymmetrization of amino diynes via hydroamination is reported.

228 tionalization of N-chlorobenzamides with 1,3-diynes via regioselective (4 + 2) annulation for the syn

229 After the corresponding 1,6-diyne was generated in situ, cyclization afforded the de

230 cyclization of 1,4-diphenyl-3-aza-3-ene-1,5-diyne was investigated.

231 pectrum of symmetrical and unsymmetrical 1,3-diynes was developed.

232 Moreover, the use of unsymmetrical diynes was investigated, resulting in the formation of t

233 or the cyclization of (3Z)-cyclodec-3-en-1,5-diyne were carried out to investigate heavy-atom tunneli

234 Many different diynes were efficiently coupled to afford [5-6-7] fused

235 ained in good yields when 1,4-diarylbuta-1,3-diynes were employed as the coupling partners.

236 t unsymmetrically substituted naphthyl-based diynes were synthesized.

237 Cyclic reactants (enynes and diynes) were readily prepared in reasonable yields from

238 the reaction of a biscarbene complex with a diyne, which generates two of the benzene rings and the

239 tation reactions of conjugated and separated diynes, which depending on the process conditions, catal

240 lyl)ethynyl)bicyclo[1.1.1]pent-1-yl)buta-1,3-diyne, whose bicyclopentane units can rotate but are ach

241 nylpyridine and a Bpin-terminated monoyne or diyne will cross-react to form benzyne intermediates.

242 roboration of benzo[3,4]cycloundec-3-ene-1,5-diyne with an N-heterocyclic carbene borane.

243 to co-cyclotrimerize long-chain alpha,omega-diynes with alkynes in certain cases to demonstrate a su

244 ar [2 + 2 + 2] alkyne cyclotrimerizations of diynes with alkynes.

245 r- and intramolecular [2+2+2] cyclization of diynes with alpha,beta-unsaturated enones proceeds with

246 regioselective cycloaddition reaction of 1,3-diynes with azide is reported to synthesize fully substi

247 cross [2 + 2 + 2] cyclotrimerizations of 1,6-diynes with cyclic and acyclic double bonds.

248 onent higher order cycloaddition of tethered diynes with cyclic trienes that generates five rings and

249 d [2+2+2] cyclotrimerizations of alpha,omega-diynes with isocyanates, isothiocyanates, and carbon dis

250 l cycloaddition reactions of substituted 1,6-diynes with maleimides have been performed.

251 zed site-selective tandem cyclization of 1,6-diynes with substituted indolines or indoles through con

252 mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of

253 amolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which give

254 Diyne + yne cycloadditions connect with arynes and ethyn

255 The first examples of 1,3-diyne + yne cycloadditions to give o-benzynes were repor